Development of Synthetic Reactions Using New Types of Lewix Acid Catalysts

使用新型 Lewix 酸催化剂的合成反应的进展

• 批准号: 08555230
• 负责人: KOBAYASHI Shu
• 金额: $ 7.55万
• 依托单位: The University of Tokyo (1998)Tokyo University of Science (1996-1997)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08555230/
• 关键词: Friedel-Crafts acylation; hafnium (IV) triflate; aldol reaction; polymer-supported catalysts; Lewis asic; scandium trifluoromethanesulfonate; aqueous reaction; bening synthesis; スカンジウムトリフラート; Friedel-Craftsアシル化; Fries転位; キノリン; アミノケトン

1.Catalytic Friedel-Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and fluorobenzene has been successfully carried out using hafnium (IV) inflate and trifluoromethanesulfonic acid as catalysts. Both aromatic and aliphatic carboxylic acid chlorides reacted smoothly under the conditions to afford the corresponding aromatic ketones in good yields.2. Metal chlorides and some perchlorates and trifluoromethanesulfonates (triflates) of group 1-15 elements were screened in the Mukaiyama aldol reaction (an aldol reaction of an aldehyde with a silyl enol ether) for the purpose of finding Lewis acid catalysts stable in water. It was shown that metal compounds based on Fe(II), Cu(II), Zn(II), Cd(II), Pb(II) as well as the rare earths (Sc(III), Y(III), Ln(III)) were stable and active in water. Correlation between catalytic activity of these elements (cations) in water and hydration constants and exchange rate constants for substitution of inner-sphere water ligands (wate … More r exchange rate constant (WERC)) were found, and without exception metal compounds, which have both pKh values from 4.3 to 10.08 and WERC greater than 3.2x10^6 M^<-1> sec^<-1>, gave satisfactory yields in the aldol reaction.3. Development of polymer-supported catalysts is one of the most important tasks in organic synthesis. especially in the move towards clean and environmentally friendly chemical processes. We have developed an unprecedented polymer-supported Lewis acid, a microencapsulated scandium trifluoromethanesulfonate (scandium inflate) (MC Sc(OTf)_3). This new method for immobilizing a catalyst onto a polymer is based both on physical envelopment by the polymer and on electronic interaction between pi electrons of benzene rings of the polymer and a vacant orbital of the Lewis acid.A scanning electron microscopy (SEM) micrograph revealed that small capsules of MC Sc(OTf)_3 adhered to each other, and it was also shown by scandium energy dispersive X-ray (EDX) mapping that Sc(OTf)_3 was located all over the polymer surface. One of the most remarkable points is that the activating ability of MC Sc(OTf)_3 was shown to be superior to monomeric Sc(OTf)_3 by preliminary kinetic studies. The catalyst was readily prepared and maintained high activity. Moreover, it was recoverable and reusable, and was successfully applied to many useful carbon-carbon bond-forming reactions. Less

1.以膨胀铪和三氟甲磺酸为催化剂，成功地进行了苯和氯苯、氟苯等未活化苯的催化傅克酰化反应，芳香族和脂肪族酰氯在一定条件下均顺利反应，得到相应的产物。芳香酮的收率良好。 2．为了寻找在水中稳定的路易斯酸催化剂，在Mukaiyama羟醛反应（醛与硅烯醇醚的羟醛反应）中筛选了1-15族元素的高氯酸盐和三氟甲磺酸盐（三氟甲磺酸盐）。基于 Fe(II)、Cu(II)、Zn(II)、Cd(II)、Pb(II) 以及稀土元素 (Sc(III)、 Y(III)、Ln(III)) 在水中稳定且具有活性。这些元素（阳离子）在水中的催化活性与内球水配体取代的水合常数和交换速率常数之间的相关性（水…更多 r 交换）。发现了速率常数（WERC）），并且无一例外地具有 pKh 值从 4.3 到 10.08 且 WERC 大于 3.2x10^6 的金属化合物M^<-1>sec^<-1>，在醛醇缩合反应中得到令人满意的产率。3．聚合物负载催化剂的开发是有机合成中最重要的任务之一，特别是在向清洁和环境友好的方向发展的过程中。我们开发了一种前所未有的聚合物支持的路易斯酸，一种微胶囊化的三氟甲磺酸钪（膨胀钪）（MC Sc(OTf)_3）。这种将催化剂固定在聚合物上的新方法是。基于聚合物的物理包封以及聚合物苯环的 pi 电子与路易斯酸的空轨道之间的电子相互作用。扫描电子显微镜 (SEM) 显微照片显示，MC Sc(OTf)_3 的小胶囊粘附在钪能量色散 X 射线 (EDX) 图也显示 Sc(OTf)_3 分布在整个聚合物表面，最引人注目的一点是，初步动力学研究表明MC Sc(OTf)_3的活化能力优于单体Sc(OTf)_3，该催化剂易于制备且保持较高的活性，并且可回收和重复使用，并已成功应用于许多领域。有用的碳-碳键形成反应较少。

项目成果

S.Kobayashi: "Facile Synthesis of α-Amino Nitriles Using Lanthanide Triflate as a Lewis Acid Catalyst" Synlett. 115-116 (1997)

S.Kobayashi：“使用镧系三氟甲磺酸盐作为路易斯酸催化剂轻松合成 α-氨基腈”Synlett 115-116 (1997)。

S.Kobayashi: "Hafnium Trifluoromethanesulfonate (Hf(OTf)_4) as an Efficient Catalyst in the Fries Rearrangement and Direct Acylation of Phenol and Naphthol Derivatives" Tetrahedron Lett.37. 2053-2056 (1996)

S.Kobayashi：“三氟甲磺酸铪 (Hf(OTf)_4) 作为弗赖斯重排和苯酚和萘酚衍生物直接酰化中的高效催化剂”Tetrahedron Lett.37。

H.Ishitani: "Catalytic Enantioselective Synthesis of a-Amino Nitriles Using a Novel Zirxonium Catalyst" Angew.Chem.Int.Ed.Engl.37. 3186-3188 (1998)

H.Ishitani：“使用新型锆催化剂催化对映选择性合成α-氨基腈”Angew.Chem.Int.Ed.Engl.37。

S.Kobayashi: "Scandium Triflate-Catalyzed Allylation Reactions of Benzoylhydrazones with Tetraallyltin. An Efficient Catalytic Route to Homoallylic Amines" Synlett.138-140 (1999)

S.Kobayashi：“三氟甲磺酸钪催化的苯甲酰腙与四烯丙基锡的烯丙基化反应。高烯丙基胺的有效催化路线”Synlett.138-140 (1999)

S.Kobayashi: "The First Catalytic Enantioselective Aza Diels-Alder Reactions of Iminodienophiles Using a Chiral Zirconium Compound" Angew.Chem.Int.Ed.Engl.37. 979-981 (1998)

S.Kobayashi：“使用手性锆化合物进行亚氨基二烯体的首次催化对映选择性 Aza Diels-Alder 反应”Angew.Chem.Int.Ed.Engl.37。